Gradient-based and wavelet-based compressed sensing approaches for highly undersampled tomographic datasets.

Electron tomography is widely employed for the 3D morphological characterization at the nanoscale. In recent years, there has been a growing interest in analytical electron tomography (AET) as it is capable of providing 3D information about the elemental composition, chemical bonding and optical/electronic properties of nanomaterials. AET requires advanced reconstruction algorithms as the datasets often consist of a very limited number of projections.

Operando Raman Spectroscopy and Synchrotron X-ray Diffraction of Lithiation/Delithiation in Silicon Nanoparticle Anodes.

Operando Raman spectroscopy and synchrotron X-ray diffraction were combined to probe the evolution of strain in Li-ion battery anodes made of crystalline silicon nanoparticles. The internal structure of the nanoparticles during two discharge/charge cycles was evaluated by analyzing the intensity and position of Si diffraction peaks and Raman TO-LO phonons. Lithiation/delithiation of the silicon under limited capacity conditions triggers the formation of "crystalline core-amorphous shell" particles, which we evidenced as a stepwise decrease in core size, as well as sequences of compressive/tensile strain due to the stress applied by the shell.

A hybrid method using the widely-used WIEN2k and VASP codes to calculate the complete set of XAS/EELS edges in a hundred-atoms system.

Most of the recent developments in EELS modelling has been focused on getting a better agreement with measurements. Less work however has been dedicated to bringing EELS calculations to larger structures that can more realistically describe actual systems. The purpose of this paper is to present a hybrid approach well adapted to calculating the whole set of localised EELS core-loss edges (at the XAS level of theory) on larger systems using only standard tools, namely the WIEN2k and VASP codes.

Nanoscale Chemical Evolution of Silicon Negative Electrodes Characterized by Low-Loss STEM-EELS.

Continuous solid electrolyte interface (SEI) formation remains the limiting factor of the lifetime of silicon nanoparticles (SiNPs) based negative electrodes. Methods that could provide clear diagnosis of the electrode degradation are of utmost necessity to streamline further developments. We demonstrate that electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM can be used to quickly map SEI components and quantify LiSi alloys from single experiments with resolutions down to 5 nm.

Multiprobe Study of the Solid Electrolyte Interphase on Silicon-Based Electrodes in Full-Cell Configuration.

The failure mechanism of silicon-based electrodes has been studied only in a half-cell configuration so far. Here, a combination of Li, F MAS NMR, XPS, TOF-SIMS, and STEM-EELS, provides an in-depth characterization of the solid electrolyte interphase (SEI) formation on the surface of silicon and its evolution upon aging and cycling with LiNiMnCoO as the positive electrode in a full Li-ion cell configuration. This multiprobe approach indicates that the electrolyte degradation process observed in the case of full Li-ion cells exhibits many similarities to what has been observed in the case of half-cells in previous works, in particular during the early stages of the cycling.

Three-dimensional analysis of Nafion layers in fuel cell electrodes.

Proton exchange membrane fuel cell is one of the most promising zero-emission power sources for automotive or stationary applications. However, their cost and lifetime remain the two major key issues for a widespread commercialization. Consequently, much attention has been devoted to optimizing the membrane/electrode assembly that constitute the fuel cell core.

Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media.

Following a well-defined series of acid and heat treatments on a benchmark Pt3Co/C sample, three different nanostructures of interest for the electrocatalysis of the oxygen reduction reaction were tailored. These nanostructures could be sorted into the "Pt-skin" structure, made of one pure Pt overlayer, and the "Pt-skeleton" structure, made of 2-3 Pt overlayers surrounding the Pt-Co alloy core. Using a unique combination of high-resolution aberration-corrected STEM-EELS, XRD, EXAFS, and XANES measurements, we provide atomically resolved pictures of these different nanostructures, including measurement of the Pt-shell thickness forming in acidic media and the resulting changes of the bulk and core chemical composition.

Growth and micromagnetism of self-assembled epitaxial fcc(111) cobalt dots.

We develop the self-assembly of epitaxial submicrometer-sized face-centered-cubic (fcc) Co(111) dots using pulsed laser deposition. The dots display atomically flat facets, from which the ratios of surface and interface energies for fcc Co are deduced. Zero-field magnetic structures are investigated with magnetic force and Lorentz microscopies, revealing vortex-based flux-closure patterns.

Multiscale tomographic analysis of polymer-nanoparticle hybrid materials for solar cells.

The present work focuses on the study of the three-dimensional (3D) morphology of polymer and nanoparticle hybrid nanocomposites used as active layers in solution-processed solar cells. The hybrid consists of blends of regioregular poly(3-alkylthiophene) and CdSe nanorods. Electron tomography (ET) analysis performed in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) allows resolving single nanorods in the hybrid blend.

Synergistic effect in carbon coated LiFePO4 for high yield spontaneous grafting of diazonium salt. Structural examination at the grain agglomerate scale.

Molecular grafting of p-nitrobenzene diazonium salt at the surface of (Li)FePO4-based materials was thoroughly investigated. The grafting yields obtained by FTIR, XPS, and elemental analysis for core shell LiFePO4-C are found to be much higher than the sum of those associated with either the LiFePO4 core or the carbon shell alone, thereby revealing a synergistic effect. Electrochemical, XRD, and EELS experiments demonstrate that this effect stems from the strong participation of the LiFePO4 core that delivers large amounts of electrons to the carbon substrate at a constant energy, above the Fermi level of the diazonium salt.

Spin fluctuations of paramagnetic Rh clusters revealed by x-ray magnetic circular dichroism.

The magnetic moment induced on Rh atoms, forming 1.6 nm average diameter clusters, embedded in an Al(2)O(3) matrix, has been determined using x-ray magnetic circular dichroism measurements. The magnetic moment varies linearly with the applied magnetic field.

Three-dimensional chemistry of multiphase nanomaterials by energy-filtered transmission electron microscopy tomography.

A three-dimensional (3D) study of multiphase nanostructures by chemically selective electron tomography combining tomographic approach and energy-filtered imaging is reported. The implementation of this technique at the nanometer scale requires careful procedures for data acquisition, computing, and analysis. Based on the performances of modern transmission electron microscopy equipment and on developments in data processing, electron tomography in the energy-filtered imaging mode is shown to be a very appropriate analysis tool to provide 3D chemical maps at the nanoscale.

Crossover from spin accumulation into interface states to spin injection in the germanium conduction band.

Electrical spin injection into semiconductors paves the way for exploring new phenomena in the area of spin physics and new generations of spintronic devices. However the exact role of interface states in the spin injection mechanism from a magnetic tunnel junction into a semiconductor is still under debate. In this Letter, we demonstrate a clear transition from spin accumulation into interface states to spin injection in the conduction band of n-Ge.

Imaging nanostructural modifications induced by electronic metal-support interaction effects at Au||cerium-based oxide nanointerfaces.

A variety of advanced (scanning) transmission electron microscopy experiments, carried out in aberration-corrected equipment, provide direct evidence about subtle structural changes taking place at nanometer-sized Au||ceria oxide interfaces, which agrees with the occurrence of charge transfer effects between the reduced support and supported gold nanoparticles suggested by macroscopic techniques. Tighter binding of the gold nanoparticles onto the ceria oxide support when this is reduced is revealed by the structural analysis. This structural modification is accompanied by parallel deactivation of the CO chemisorption capacity of the gold nanoparticles, which is interpreted in exact quantitative terms as due to deactivation of the gold atoms at the perimeter of the Au||cerium oxide interface.

Micromagnetic study of flux-closure states in Fe dots using quantitative Lorentz microscopy.

A micromagnetic study of epitaxial micron-sized iron dots is reported through the analysis of Fresnel contrast in Lorentz Microscopy. Their use is reviewed and developed through analysis of various magnetic structures in such dots. Simple Landau configuration is used to investigate various aspects of asymmetric Bloch domain walls.

Luminescence of polyethylene glycol coated CdSeTe/ZnS and InP/ZnS nanoparticles in the presence of copper cations.

The use of click chemistry for quantum dot (QD) functionalization could be very promising for the development of bioconjugates dedicated to in vivo applications. Alkyne-azide ligation usually requires copper(I) catalysis. The luminescence response of CdSeTe/ZnS nanoparticles coated with polyethylene glycol (PEG) is studied in the presence of copper cations, and compared to that of InP/ZnS QDs coated with mercaptoundecanoic acid (MUA).

Dimensionality crossover in magnetism: from domain walls (2D) to vortices (1D).

Dimensionality crossover is a classical topic in physics. Surprisingly, it has not been searched in micromagnetism, which deals with objects such as domain walls (2D) and vortices (1D). We predict by simulation a second-order transition between these two objects, with the wall length as the Landau parameter.

Lorentz microscopy mapping for domain wall structure study in L1(0) FePd thin films.

Thin film alloys with perpendicular anisotropy were studied using Lorentz transmission electron microscopy (LTEM). This work focuses on the configuration of domain walls and demonstrates the suitability and accuracy of LTEM for the magnetic characterization of perpendicular magnetic anisotropy materials. Thin films of chemically ordered (L1(0)) FePd alloys were investigated by micro-magnetic modeling and LTEM phase retrieval approach.

Quantitative observation of magnetic flux distribution in new magnetic films for future high density recording media.

Off-axis electron holography was used to observe and quantify the magnetic microstructure of a perpendicular magnetic anisotropic (PMA) recording media. Thin foils of PMA materials exhibit an interesting up and down domain configuration. These domains are found to be very stable and were observed at the same time with their stray field, closing magnetic flux in the vacuum.

Controlled switching of Néel caps in flux-closure magnetic dots.

While magnetic hysteresis usually considers magnetic domains, the switching of the core of magnetic vortices has recently become an active topic. We considered Bloch domain walls, which are known to display at the surface of thin films flux-closure features called Néel caps. We demonstrated the controlled switching of these caps under a magnetic field, occurring via the propagation of a surface vortex.

High-Curie-temperature ferromagnetism in self-organized Ge1-xMnx nanocolumns.

The emerging field of spintronics would be dramatically boosted if room-temperature ferromagnetism could be added to semiconductor nanostructures that are compatible with silicon technology. Here, we report a high-TC (>400K) ferromagnetic phase of (Ge,Mn) epitaxial layer. The manganese content is 6%, and careful structural and chemical analyses show that the Mn distribution is strongly inhomogeneous: we observe eutectoid growth of well-defined Mn-rich nanocolumns surrounded by a Mn-poor matrix.

Electron spectroscopy imaging to study ELNES at a nanoscale.

Series of energy-filtered TEM images have been acquired with very narrow energy slit using a post-column energy filter. This allowed us to reconstruct spectra with an energy resolution estimated to 2 eV, and a spatial resolution in the order of 0.5 nm.